Process of desulphurizing hydrocarbon oils



Patented Feb. 25, 1941 PAT N OFFIEE 2,232,971 rnocnss or DESULPHURIZ'INGHDR0+ p CARBON OILS Elmer H. Records and James-1i; state retains,

Wash.

No Drawing. Application June 6, 1939, Serial No. 277,646

3 Claims. (01. 196-24) This invention relates to methods of makingchemical mixtures, and comprises a process of making a highly reactivechemical mixture, which, if added to hydrocarbon oils and thecombination heated under pressure, combines or reacts upon the sulphurcompounds in thehydrocarbon oils so treated in sucha manner that gaseoussulphur compounds and water soluble sulphur compounds are formed whichmay be easily eliminated, resulting in a distinct improvement of thehydrocarbon oil under treatment.

We have discovered that when certain solid and liquid chemicals arecombined, and added in proper proportions to liquid hydrocarbons, thenheated under pressure, and subsequently cooled, such chemicalcombination has the characteristic of becoming completely absorbed bythe liquid hydrocarbon, and in such manner that the sulphur compoundscontained in the liquid hydro carbon are converted and may be easilyremoved. We have also found that, by use of this chemical mixture, allthe ingredients used in said mixture, each of which is known to bebeneficial in the treatment of hydrocarbon oils, are completely absorbedinto the oil incident to the heat treatment under pressure. This is ofdistinct advantage in that there is no waste in unabsorbed chemicals,and is also a distinct departure from the use of certain chemicals whichare used to react upon hydrocarbon oils catalytically.

Ordinarily in treating hydrocarbon oils for desulphurizing, catalyticmetals or salts are used, but we have found by the use of thecombination of chemicals herein cited that they are completely absorbedinto the oils being treated, although several of the chemicals used insaid combination are not normally soluble in liquid hydrocarbons. By ourcombination we have discovered thatby heating under pressure, each ofthe ingredients, all beneficial to the treatment of hydrocarbon oils,combine easily by solution or dissociation into the hydrocarbon oilunder treatment, and have the added attribute of reacting upon sulphurcompounds in such a manner that they are easily removed both in gaseousform and by simple water wash without the use of caustic or acid.

The process of sulphur removal is therefore much simpler and cheaperthan are the methods in common use wherein a portion only of the sulphurcompounds in the oil is removed by alkali or acid washes.

By experiment we have found our mixture effective for sulphur reductionupon hydrocarbon oils of many varieties, such as crude petroleum oil,residuum oil, tar-oils, shale oil and various pyrobitumens.

We have found that a mixture such as ours, of high reactivity with thesulphur compounds of hydrocarbon oils can be prepared by using in thefollowing proportions the following easily obtained chemicals:

For each gallon, of hydrocarbon oil processed, add:

Ferric chloride (FeCla) grams 40 Arsenic acid (AS205) do 8 Napthalene"do"-.. 8 Barium chloride do 4 Alcohol (methyl or ethyl) cc 100 Benzolcc 40 Alum grams 4 Other forms of arsenic and barium may be substitutedfor those given above, such as arsenic chloride, arsenic chlorideammonium, arsenic trifluoride, arsenic diiodide or triiodide; or bariumbromide, barium hydroxide, barium iodide and barium oxide.

In preparing the mixture, we prefer to dissolve the naphthalene andferric chloride in the alcohol and benzol solution, then to mix thiscombination with the oil to be treated and the dry ingredients arsenic,alum and barium added thereto.

Although the proportions given above are cited as an example fortreating petroleum containing sulphur compounds to the extent of theproportions so cited are not arbitrary, as the various ingredients maybe changed and varied as to weight and volume in ratio to the sulphurcontent of the oil under treatment, although the chemical combinationshould be retained as to the chemicals used.

It has been found also that the amount of chemical per unit of oiltreated may be varied to procure the desired desulphurization with oilsof varying sulphur content.

The mixture afterpreparation as cited above is added to the oil to bedesulphurized, thoroughly mixed by suitable means, the mixture placed inany suitable vessel wherein the temperature and pressure may be raisedin the absence of air. After such heating, it will be found thatsulphurated hydrogen and sulphur dioxide in large volume will be givenoff the treated oil upon release of the pressure back to atmosphericpressure.

The treated oil may be further purified by washing with water insuitable equipment and thence distilled into valuable hydrocarbon oils,substantially free of sulphur compounds, without prior treatment ofalkalis or acids.

Having thus described our invention, what we claim as new therein anddesire to secure by Letters Patent isv 1. The process of desulphurizinghydrocarbon oils comprising mixing with a quantity of oil atreating'mixture comprising ferric chloride, ar-H senic acid,napthalene, barium chloride, alum," alcohol and benzol, and then heatingthe mixed oil and treating mixture under pressure 5 2. The process ofdesulphurizinghydrocarbon

